Dinitrophenylenediamines as herbicides

ABSTRACT

Compounds of the formula below are useful as herbicides WHEREIN X, Y and Z are substituents independently selected from the group consisting of nitro, fluorine, chlorine, bromine, iodine, hydrogen, and alkyl of 1 to 12 carbon atoms, provided that at least two of said X, Y and Z substituents are nitro; A, B, C and D are substituents independently selected from the group consisting of hydrogen, alkyl of 1 to 12 carbon atoms and alkenyl of 2 to 12 carbon atoms, provided that at most 3 of said A, B, C and D substituents are hydrogen, and further provided that at least one of said A, B, C and D substituents is an alkyl or alkenyl group of from 2 to 12 carbon atoms.

United States Patent 1 91 Linder et al.

[ 1 DINITROPHENYLENEDIAMINES AS HERBICIDES [75] Inventors: Jerome Linder, Westfield, N.J.;

Edward D. Weil, Hastings-on-Hudson, NY.

[73] Assignee: Hooker Chemicals & Plastics Corporation, Niagara Falls, NY.

[22] Filed: Feb. 27, 1970 [21] App1.No.: 15,301

Related US. Application Data [63] Continuation-in-part of Ser. No, 577,154, Sept. 6,

1966, abandoned.

[52] US. Cl. 7l/l21; 260/577; 260/578 [51] Int. Cl A01n 9/20 [58] Field of Search 71/121; 260/577 [56] References Cited UNITED STATES PATENTS 11/1963 Soper 71/121 3,121,116 2/1964 Pawloski.. 71/121 3,257,190 6/1966 Soper 71/121 3,442,639 5/1969 Soper 71/121 3,449,111 6/1969 Wright 71/121 3,530,184 9/1970 Minieri et a1. 71/121 1451 July 22,1975

Primary Examiner--Glennon 1-1. l-lollrah Attorney, Agent, or Firm-Peter F. Casella; John M. Petruncio [5 7 ABSTRACT Compounds of the formula below are useful as herbicides wherein X, Y and Z are substituents independently selected from the group consisting of nitro, fluorine, chlorine, bromine, iodine, hydrogen, and alkyl of 1 to 12 carbon atoms, provided that at least two of said X, Y and Z substituents are nitro; A, B, C and D are substituents independently selected from the group consisting of hydrogen, alkyl of l to 12 carbon atoms and alkenyl of 2 to 12 carbon atoms, provided that at most 3 of said A, B, C and D substituents are hydrogen, and further provided that at least one of said A, B, C and D substituents is an alkyl or alkenyl group of from 2 to 12 carbon atoms.

4 Claims, No Drawings DINITROPHENYLENEDIAMINES AS HERBICIDES CROSS REFERENCES This application is a continuation-in-part of Ser. No. 577,154, filed Sept. 6, 1966 now abandoned.

This invention relates to novel dinitrophenylenediamines and the herbicidal uses thereof.

In accordance with this invention, there is provided a compound of the formula:

wherein X, Y and Z are substituents independently selected from the group consisting of nitro, fluorine, chlorine, bromine, iodine, hydrogen and alkyl of l to 12 carbon atoms, provided that at least two of said X, Y and Z substituents are nitro, R is of the formula:

and R is of the formula:

on N

wherein A, B, C and D are substituents independently selected from the group consisting of hydrogen, alkyl of l to 12 carbon atoms and alkenyl of from 2 to 12 carbon atoms, provided that at most 3 of said A, B, C and D substituents are hydrogen, and further provided that at least one of said A, B, C and D substituents is an alkyl or alkenyl group of from 2 to 12 carbon atoms. In a preferred embodiment of the invention, Y and Z are nitro, and X is selected from the group consisting of chlorine and methyl. In one of the more preferred embodiments of the invention, Y and Z are nitro, X is selected from the group consisting of chlorine and methyl, A and B are independently selected from the group consisting of hydrogen, alkyl of l to 4 carbon atoms and alkenyl of from 2 to 4 carbon atoms, and C and D are hydrogen. In another of the more preferred embodiments of the invention, Y and Z are nitro, X is selected from the group consisting of chlorine and methyl, and A, B, C and D are independently selected from the group consisting of hydrogen, ethyl, n-propyl, isopropyl, and sec-butyl, provided that no more than one substituent selected from the group consisting of isopropyl and sec-butyl may be bonded to any one nitrogen atom.

The compounds of this invention provide a novel process for the control of grasses and broadleaf plants and weeds when applied in a herbicidally effective amount to the locus of said plants either prior to or after germination. When so applied at an application rate of from about 0.2 to 100 pounds per acre, perferably at a rate of from about I to about 16 pounds per The herbicidal compounds of this invention can be used alone or as part of solid or emulsified formulations of various types. They may be formulated as emulsifiable concentrates or wettable powders for sprays, as granules, or as dispersions on carriers such as peat moss or vermiculite. Because said compounds are relatively insoluble in water, it is preferred to use a wetting agent in the formulation thereof.

The compounds of this invention were prepared by three methods which, for the purpose of convenience in referring to Table l, which describes the preparation and properties of said compounds, will be referred to as methods A, B and C. In method A, a mixture of one mole of a halogenated aromatic compound (whose structure is defined by the substituents of One of the Reactants column of Table l) and an amine (whose structure and concentration is defined by the Other Reactants and Concentrations Thereof" column of said Table), and a solvent quantity centimeters of ethanol were placed in an autoclave, heated to the temperature specified in the Temperature" column of Table l, and kept at said temperature for a period of time defined by the Time in Hours column of Table I. Thereafter, the autoclave was opened, the contents thereof were evaporated to dryness, extracted with a solvent quantity of benzene, and washed with water to remove amine hydrochloride. The benzene solution was evaporated to dryness, yielding a solid which then recrystallized by the solvent specified in the Solvents Used for Crystallization column of Table I, yielding a compound with the physical properties specified in Table I. In method B one mole of the chlorinated aromatic compound was dissolved in a solvent quantity of refluxing ethanol. To this solution was added the amine, and the mixture was heated at the specified temperature for the specified time. The entire contents were then evaporated to dryness, extracted with a solvent quantity of benzene and washed with water. The benzene solution was evaporated to dryness yielding a solid which was then recrystallized by the specified solvent. In method C, one mole of the chlorinated aromatic compound was added slowly to the specified amount of the specified amine. The mixture was then heated for the specified time at the specified temperature, and the recovery procedure or method B was thereafter used.

After said compounds were prepared, they were subjected to herbicidal testing. Sandy topsoil was run through a 30 mesh sieve. The sieved topsoil was then poured into 14 inches X 20 inches X 4 inches wooden flats until it was three-fourths inch from the tops thereof, and was moistened. The crops to be tested were then planted in rows in said flats, said rows equidistant from each other. One-half inch of the topsoil was then added to said flats, and the weeds to be tested were then planted in rows in said flats. One-quarter inch of topsoil was then added to said flats, the soil in said flats was then moistened. For pre-emergence testing, chemicals to be tested were sprayed onto said soil at the specified concentrations immediately after the planting of said crops and weeds. For post-emergence testing, said chemicals were sprayed onto said flats from 7 to 10 days after planting, when the crops and weeds had emerged. The results of both preand postemergence testing appear in Table l. The preand postapplication rate is given in pounds per acre. The results are on a scale from O-lO, wherein 0 equals 0 percent kill and 10 equals percent kill.

3 89 5 ,9 3 4 3 4 To more specifically illustrate the invention, th folnot to be deemed [imitative of the invention, are preslowing examples, which are merely illustrative and are ented in Table 1.

Table l Solvents Substituents On Other Reactants Time Ised Fpr Prepar- M l d One Of The And Relative ln Temperysta ation e ting s b t r ie Reactants Amounts Thereof Hours rature lization Method Point Ex. R R E J K L I N C H C] Cl Cl NO 10M, (C H NH 24 Reflux CH OH C 71-3C gffi gfls Nik Cl N NH CH: M, CJ-liNilZ-sec l2 Reflux Eth anol B l54-6C Nitrogcn/ Color Chlorine Empirical Application Millet Cabbage Crab- Tot- Rye Cugmm- P gma 0 er Yield Found Formula Rate Grass weed Alfalfa 15.6 9.9 C CIN 0 Pre 8 l0 0 l0 0 l0 0 1 Yellow 66 21 4 4 Post 4 0 0 8 0 4 2 E C H 0 Pre 2 l0 0 l0 0 2 Orange 90 8/ 11 I5N4 4 Pre 4 9 l0 0 lo 2 8 Post 2 0 8 0 2 2 l0 Post 4 2 l0 0 7 2 l0 Solvents Substituents On Other Reactants Time T lsed Fpr Prepar- M l C nd One Of The And Relative n emperysta ation e ting 8' d Reactants Amounts Thereof Hours rature lization Method Point Ex. R R E J K L 3 N(C2H5)2 Nl-l Cl NO NH CH 5M, (C H ),NH l2 Reflux Ethanol B 108-1 1 1C 4 H NH Cl NO, NH, CH 5M, (nC H ),Nl-l 12 Reflux Ethanol B 129-30C 5 me l-1 N(C H n) Cl N0 0! CH 10M, (nC H ),Nl-l 48 150C 0 1 A 6 Nl-lC l-l n NHCJ-h-n Cl N0 C] CH; 6M, (nc l'lfl Nl l 48 1602C O l A 7 N(C H N(C,l-l Cl N0 Cl CH 6M, (C HQ NH 48 160 C Oil A Nitrogen/ Color Chlorine Empirical Application Millet Cabbage Crab- Tot-o Rye culfeum- Pigma r Yield Found Fonnula Rate grass weed Alfalfa 3 Orange 98 20.3/ C l-l N.O Pre 2 6 9 0 l0 2 8 Pre 4 10 l0 0 l0 0 10 Post 2 3 8 0 0 5 l0 Post 4 4 l0 2 0 4 l0 4 Orange 98 18.3/ C H N O Pre 2 9 9 0 9 0 3 Pre 4 l0 9 0 l0 0 l0 Post 2 3 l0 0 5 5 l0 Post 4 4 9 4 5 6 l0 5 Brownish 98 14.4/ C u mm Pre 4 7 3 3 9 0 l0 Yellow Post 4 6 6 0 0 2 0 6 Brownish 95 C H N O Pro 4 0 0 0 0 0 0 Black Post 4 6 2 2 0 2 0 7 Brownish 71 l6.9/ C -J-I N O Pre 4 l0 3 0 l0 4 l0 Yellow Post 4 6 I 6 0 4 0 0 Solvents Substituents On Other Reactants Time Used For Prepar- Substituents On Compound One Of The And Relative in Tempe- Crystalation Melting Obtained Reactants Amounts Thereof Hours rature lization Method Point Ex. R R E J K L I 8 N(Cl'l N(Cl-l,,) Cl NO, C] CH; 6M, (Cl-l hNl-I l2 l-l60C l-lexane A -7C 9 Nl-l Nl-l Cl NO Cl CH NH; 24 150C A 262C 10 Nl-lC l-l n Nl-l Cl NO, Nl-l Cl-l, 1M, nCJ-bNH, l2 Reflux Benzene B l25-9C ll N(CH; N(Cl-l,,) Cl NO C1 C1 9M, (CH;,),NH l2 C Hexane A 779C l2 N(CH5)2 N(CH5)z Cl NO Cl Cl 10M, (C HQ NH 12 Reflux CH OH C 9l3C Nitrogen] Color Chlorine Empirical Application Millet Cabbage Crab- Io- Rye Cueum- Pigmato ber Yield Found Formula Rate grass weed Alfalfa 8 Yellow 78.5 20.9/ C l-I N O Pre 4 I 10 2 0 9 l0 4 Post 4 0 0 0 0 0 0 9 Yellow 50 26.7/ C-,l-i ,N.,O Pre 4 2 8 0 6 0 0 Post 4 4 9 2 0 2 0 10 Orange 10 2l.8/ C l-l N O Pre 4 l0 3 9 8 5 l0 Post 4 5 8 0 0 4 0 ll Dark 84 18.83/12.l C ll,;,ClN O Pre 8 l0 0 0 8 0 0 Tan Pre l6 l0 0 0 l0 0 Post 4 0 0 0 0 0 0 12 Yellow 69 15.6/ 10.0 C I-[ 31N 0 Pre 8 8 0 0 8 0 3 0 To- Rye Cucum- Pigmato ber weed Alfalfa Table l -Continued 7: Nitrogen/ Color 71 Chlorine Empirical Application Millet Cabbage Crab- Yield Found Fonnulu Rate Grass Post 4 Pre 1 Pre 2 Pre 4 Pre l6 Melting Point Solvents Used For Prepar- In Tempe- Crystalation Hours rature lization Method 1 2 Reflux Hexane B 16 100C Hexane A l 2 Reflux Ethanol B Reflux Hexane B l 2 Reflux Hexane- B Benzene l 2 Reflux Substituents On Other Reactants Time Substituents On Compound One Of The And Relative Obtained Reaetants Amounts Thereof NHC(CH NHC(CH Cl N0 Cl Cl 10M,

4H1 z N(C H-,-n), N(CH,) N(C H N0 Cl Cl 3M, (Cl-l hNH )2 l5 N(C,H -sec) NH, Cl NO, NH Cl 3M,

4H0)2 N(CH CH= NH Cl N0 NH; 3M,

2): (CH =CHCH ),NH l7 NHCJb-sec NH Cl NO NH: 3M,

sec C H NH NH Cl NO, NH, 3M,

NH CH CH OH Color Yield Chlorine Formula Rate Found l8 NHCH CH OH 1 24 4 8 4 4 eenfiefl emenefle r Ph m mhhh mh mnn mh 4 4 4 p 1 1 1 o m m m m m c a c a. n m a finial C C C C C C 2 2 l 8 w w m H 2 2 u u w 6 5 m 7 9 O. l l U l l 2 0 5 8 4 M M M m h h h w .mw e .mw ww m om l ml i e dr adadd Y TYO TYTYY B M 5 6 7 8 Post 4 Substituents On Other Reactants Time Solvents One Of The And Relative In Tempe- Used For Prepar- Reactants Amounts Thereof Hours rature Crystalation Melting lization Method Point Cl NO, NH Cl 3M nC H NH, l2 Reflux Ethanol Cl NO Nl-I Cl 3M isoC;H-,NH 48 Reflux CH,OH Cl NO NH, Cl 3M (nC HmNH l2 Reflux Ethanol Cl NO, NH, (nC,H-,) NH l2 Reflux Ethanol Cl NO, NH, Cl 3M (C Hg NH l2 Reflux Ethanol Empirical Application Millet Cabbage Crab- To- Rye Cucurn- Pig- Alfalfa mato ber Formula Rate grass weed Substituents On Compound Obtained l9 NHC H n NH, 20 NHCqHr-iSQ NH, 21 N(C H,n), NH, N( a 1-' )2 (C H NH Color Yield Nitrogen/ Chlorine Found 00069009050 11 .ll 1 .l

4 4 1 1 D D 4 1 N N m m m c t m m a a n. 1 m c c c c C 9 8 2 2 l U 2 0 L 1 1 1 1 a w 6 7 8 2 1 1 1 5 0 4 5 5 9 8 8 8 9 e e e e 1 mum mom a amamdmm Y Y0Y0Y00 9 0 ll 2 3 I 2 2 2 2 Solvents Used For Prepar- Tempe- Crystalation Melting rature lization Method Point Time In Substituents On Other Reactants One Of The And Relative Reactants Amounts Thereof Hours Substituents On Compound Obtained Table l Cntinued Ex. R R E J K L 24 NH; N(C H n) NH, N0 Cl Cl 3M, (nC H NH l2 Reflux Hexane B 73-5C 25 NH, N(C H NH; N0 Cl Cl 3M, (C HQ NH l2 Reflux Hexane B 768C 26 NH, N(C H l) NH N0 Cl C] 3M, (isoC l-l NH l2 Reflux Hexane- B 84-6C Benzene 27 N(C l-l N(C,H N(C H N0 Cl Cl 0.3M, C H NH 100C CH OH A 79.5-82C 28 N(C H,,) N(CH=,) N(C H NO, Cl Cl 10M, (CH ),NH l2 100C CH OH A 7274C Color Nitrogen/ Empirical Application Millet Cabbage Crab- To- Rye Cucum- Pigmato b Yield Chlorine Formula Rate grass er weed Alfalfa Found 24 Orange 80 l7.6/1l.l C H ,ClN,O Pre 4 8 6 0 7 0 0 Post 4 5 8 5 0 7 0 Orangish 86 l9.l/l2.2 C H ClN O Pre 4 9 7 0 9 0 0 Brown Post 4 0 9 3 O 4 0 26 Yellowish 81.5 16.1/10.5 C H CIN O Pre 4 7 4 0 5 0 l0 Bronze Post 4 6 7 0 0 2 0 27 Yellow 48 17.45/] L! C I-[ 6N 0 Pre 8 7 0 0 7 0 0 Post 4 O 3 3 0 3 0 28 Yellow 43 16.8/ 11.0 C I-[ 0N 0 Pre 8 l0 5 0 0 0 0 Post 4 0 0 0 O 3 0 R 0 Cl 2 The compound of Example 1 is of the formula The compounds of Examples 1 l 28 are of these compounds, are defined in the table.

This reactant is of the formula L J each instance, the amount each instance, the amount K Preparation methods A, B, and C as described on page 3.

The compoundsof Examples 2 10 are of the formula the formula, wherein R and R, the substituents on wherein E, J, and L are substituents defined in the table. In of the reactant 180118 mole. (see footnote 4, infra).

This column indicates the amount of amine reactant used in relation to the amount of aromatic reactant used, but does not give the absolute concentration of either. Thus the IOM" of Example 1, e.g., indicates that for every mole of aromatic reactant used ten moles of amine reactant were used."

Herbicidal compositions employing the compounds of the present invention may be combined with a variety of adjuvants such as formulation adjuvants selected from the group consisting of solvent, liquid carrier and solid carrier. For a more thorough discussion of formulation adjuvants, see US. Pat. No. 3,482,019.

Although the above examples and descriptions of this invention have-been very specifically illustrated, many I other modifications will suggest themselves to those skilled in the art upon a reading of this disclosure. These are intended to be comprehended within the scope of this invention.

What is claimed is:

1. A method for controlling weeds comprising applying, to the locus to be controlled, a herbicidal amount of a compound of the formula in which Z is lower alkyl, each R is selected from group consisting of hydrogen and lower alkyl.

the

2. The method for controlling weed .growth which O2N Cl in which each R is selected from the group consisting of hydrogen and lower alkyl, at least one of said R's being a lower alkyl. 

1. A METHOD FOR CONTROLLING WEEDS COMPRISING APPLYING, TO THE LOCUS TO BE CONTROLLED, A HERBICIDAL AMOUNT OF A COMPOUND OF THE FORMULA
 2. The method for controlling weed growth which comprises applying to the locus of said weeds a phytotoxic amount of the compound N3, N3-diethyl-2,4-dinitro-6-chloro-1,3-phenylenediamine.
 3. The method for controlling weed growth which comprises applying to the locus of said weeds a phytotoxic amount of the compound N3, N3-di-n-propyl-2,4-dinitro-6-chloro-1,3-phenylenediamine.
 4. A METHOD FOR CONTROLLING WEEDS COMPRISING APPLYING, TO THE LOCUS TO BE CONTROLLED, A HERBICIDAL AMOUNT OF A COMPOUND OF THE FORMULA 